The present invention relates to new form constructions and digital printable releasing coating compositions useful thereto.
Validation stickers are used as proof of registration of automobiles and other articles (e.g., trucks, snowmobiles, etc.) These retroreflective stickers generally have a printable plastic top surface and a pressure sensitive adhesive (PSA) on the bottom with a protective liner that is removed before it is adhered to the ultimate surface such as an automobile license plate. These stickers usually have variable information that is printed using screen printing, letter press, offset, laser or thermal transfer printing technologies. The end user (e.g., automobile owner) typically also gets a card with his/her address, insurance information, amount paid, etc., at the time the fees are paid to the issuing agency, typically a Department of Motor Vehicles Agency of the State Government. More and more these agencies like to process these stickers and cards at the same time and on demand as needed. So stickers with the liners are pre-attached to cards via an additional layer of adhesive between the liner and the card surface prior to the printing operation. There are some problems, however, with this approach, and they include: (1) an extra layer of an adhesive is needed which adds to cost of sticker; (2) a sticker with a liner on paper makes the area containing the sticker much thicker than the rest of the paper creating media jamming problems in a printer; and (3) because of the added thickness of a sticker, it gets picked off at idlers in a printer or when it goes through a fusing area in a laser printer. In terms of the paper surface, it has to be print-receptive for different types of marking materials. For example thermal transfer printing requires a special coating be put on the paper surface before the sticker is placed on it so that the paper surface can be printed on.
Thus, there is a need for a form construction with a signage such as a sticker in which an additional liner with an additional adhesive is eliminated so that it is economical and the form with the signage can be printed in a digital printer (such as a laser printer or an ink-jet printer) and the problems as above are removed.
In accordance with a first aspect of the present invention, there is provided a novel filling-in form construction that includes a substrate having a digital printable surface portion and a release coating surface portion, on which release coating surface portion a signage with a pressure sensitive adhesive can be releasably adhered.
In accordance with a second aspect of the present invention, there is provided a filling-in form construction that includes a substrate having a digital printable surface portion and a release coating surface portion, and a signage article having a pressure sensitive adhesive on one surface thereof and adhered to the release coating surface portion of the substrate by the adhesive. Preferably, the signage article comprises a retroreflective sheeting and may be a part of a validation sticker.
In accordance with a third aspect of the present invention, there is also provided a digital printable release coating composition comprising a copolymerization product (I) of (a) 25 to 70% by weight of at least one ester of acrylic acid or methacrylic acid with a long chain alkyl terminated primary alcohol, wherein the terminal alkyl chain is from 12 to 22 carbon atoms in length; (b) 4 to 15% by weight of at least one carboxylic acid functional monomer; and (c) 15 to 60% by weight of at least one free radically polymerizable monomer.
The digital printable release coating composition may preferably be a blend of the copolymerization product (I) and at least one silicone/acrylate copolymer (II) in a ratio of the blend of (I)/(II) in a range of not more than 90/10, preferably between 90/10 to 60/40, more preferably between 85/15 to 65/35, most preferably between 80/20 to 70/30.
A preferable silicone/acrylate copolymer (II) is as described in U.S. Pat. No. 5,032,460, which is herein incorporated by reference. A preferred copolymer has the formula: 
wherein
R1 are monovalent moieties which can independently be the same or different which are selected from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, and hydrogen;
R2 and R4 are divalent linking groups which can independently be the same or different and include, but are not limited to, C1 to C10 alkylene, arylene, alkylarylene and alkoxyalkylene;
R3 are monovalent moieties which can independently be the same or different which are selected from the group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino, hydroxyl and fluoroalkyl, and hydrogen;
x is an integer of 0-3;
y is an integer of preferably 10 or greater;
q is an integer of 0-3; and
G5 and G6 are monovalent moieties which can independently be the same or different selected from the group consisting of alkyl, aryl, alkylaryl, alkoxy, alkylamino, fluoralkyl, hydrogen, and xe2x80x94WSA;
W is a divalent linking group;
A is a polymeric segment or block consisting essentially of polymerized free radically polymerizable monomer; and
G2 and G4 are the same or different and comprise A.
Another preferable silicone/acrylate copolymer (II) is described in U.S. Pat. No. 5,154,962, which is herein incorporated by reference. One preferred copolymer is a copolymer of D and E monomers copolymerized to form a polymeric backbone with F monomer grafted thereto, wherein
D is at least one free radically polymerizable monomer;
E is at least one polar monomer copolymerizable with D, the amount of E being up to 30% of the total weight of all monomers, and
F is a monomer having the general formula:
Xxe2x88x92(Y)nSiR(3xe2x88x92-m)Zm
wherein
X is a group copolymerizable with the D and E monomers,
Y is a divalent linking group where n is zero or 1;
m is an integer of from 1 to 3;
R is suitably hydrogen, lower alkyl (e.g., methyl, ethyl, or propyl), aryl (e.g., phenyl or substituted phenyl), or alkoxy; and
Z is a monovalent siloxane polymeric moiety having a number average molecular weight above about 1,000 and is essentially unreactive under copolymerization conditions.
The digital printable release coating composition may alternatively be a blend of the copolymerization product (I) and at least one silicone containing release agent (III), preferably a premium release polydimethyl siloxane, in a ratio of the blend of (I)/(III) in a range of not more than 90/10, preferably between 90/10 to 50/50, more preferably between 60/40 to 50/50.
Suitable silicone release agents include conventional silicone containing release coatings used in the pressure sensitive adhesive art. Suitable agents are described, for example, in U.S. Pat. No. 5,576,356, which is herein incorporated by reference. Typically preferred such agents include polymeric silicone containing coatings that by themselves provide a release surface for typical pressure sensitive adhesives.
One suitable silicone release agent is made by processing polydimethyl silanol solution (e.g., SS-4191 A, available from GE Silicone), tin catalyst solution (SS-4192 C, available from GE Silicone), dimethyl amino propyl silane (e.g., SS-4259 C, available from GE Silicone) and calcofluor white fluoroescent dye (e.g., Blankophor 5% available from Bayer). The resulting mixture suitably may be adjusted to approximately 5% solids in toluene before coating on a substrate. The digital printable release coating composition may alternatively be a blend of the silicone/acrylate copolymer (II) and at least one silicone containing release agent (III), preferably a premium release polydimethyl siloxane, in a ratio of the blend of (II)/(III) in a range of not more than 90/10, preferably between 90/10 to 70/30, more preferably between 80/20 to 75/25. In a further aspect of the present invention, there is provided a filling-in form construction that includes a substrate having a digital printable release coating surface portion and a signage article having a pressure sensitive adhesive on one surface thereof and adhered to the release coating surface portion of the substrate by the adhesive, wherein the digital printable release coating surface portion has a coating comprising the chemical composition of the third aspect of the present invention.